Modified polyphenylene ether resin

ABSTRACT

Provided is a modified polyphenylene ether resin which is a reaction product of 100 parts by weight of (A) a polyphenylene ether having a main chain structure of the following formula (1): 
                 
 
(wherein R 1  and R 4  each independently represents hydrogen, a primary or secondary lower alkyl, a phenyl, an aminoalkyl or a hydrocarbonoxy, and R 2  and R 3  each independently represent, hydrogen, a primary or secondary lower alkyl or a phenyl), and 0.01 to 10.0 parts by weight of (B) a modifier selected from conjugated non-aromatic diene compounds, dienophilic compounds having one dienophile group and precursors of the diene or dienophilic compounds, wherein the number of rearrangement structures each represented by the following formula (2): 
                 
 
(wherein R 1 , R 2 , R 3 , and R 1  have the same meanings as defined above in the formula (1)) is less than 0.01 per 100 phenylene ether units of the formula (1). The resin has sufficient functionality and is well balanced between color tone/appearance and heat resistance/mechanical physical properties.

TECHNICAL FIELD

The present invention relates to a modified polyphenylene ether resinusable as a plastic material or a modifier therefor in theelectric/electronic fields, automotive field, various other industrialmaterial fields or food/package fields; and a preparation process of it.

BACKGROUND ART

Since polyphenylene ethers are excellent in processability andproductivity products/parts of any shape can be produced efficientlyfrom them by melt injection molding, melting extrusion or the likemethod. They are therefore widely used as a material for products/partsin the electric/electronic fields, automotive field, various otherindustrial material fields, or food/package fields.

With a recent tendency to produce a variety of products/partsparticularly in the electric/electronic fields, automotive field orvarious other industrial fields, a demand for resin materials has cometo be wider.

In order to satisfy this demand, resin materials imparted with such aproperty as have not been attained by the existing materials so far aredeveloped by forming a composite from different materials or by apolymer alloy technique to use various existing polymer materials incombination.

Although ordinarily employed polyphenylene ethers have high heatresistance and excellent mechanical properties, materials to form acomposite with polyphenylene ethers are limited owing to their pooraffinity with another material. Affinity with a highly polar materialsuch as polyamide is particularly poor so that a modified polyphenyleneether resin having functionality with a polar group is required uponformation of a composite with such a resin.

As means for obtaining a modified polyphenylene ether resin, chemicalmodification, in a molten state, of a polyphenylene ether orpolyphenylene-ether-containing resin composition with a compound havinga polar group is under investigation.

For example, proposed in JP-B-3-52486 (the term “JP-B” as used hereinmeans an “examined published Japanese patent publication”), U.S. Pat.No. 4,654,405, U.S. Pat. No. 4,888,397 or JP-A-63-54425 (the term “JP-A”as used herein means an “unexamined published Japanese patentapplication) is a process for obtaining a modified polyphenylene etherresin by mixing a polyphenylene ether with maleic anhydride or anotherreactive compound for modification in the presence or absence of aradical initiator, and kneading the mixture in a molten state, therebymodifying the polyphenylene ether in a molten state.

The above-described process however causes various problems, becausekneading of the polyphenylene ether in a molten state requires hightemperature and the melt viscosity of the polyphenylene ether is veryhigh, which inevitably cause a marked rise in the reaction temperature.

In other words, a modified polyphenylene ether resin obtained by theconventional melt kneading method is processed at almost thedecomposition temperature so that a color change due to thermaldeterioration occurs and the modified polyphenylene ether resin thusobtained involves a problem in its color tone/appearance.

In order to overcome the above-described problem in colortone/appearance, proposed is a process for melt extrusion of a mixtureof a polyphenylene ether and an additive such as heat stabilizer andantioxidant. This process however fails in sufficient improvement incolor tone/appearance because the temperature upon melt kneading isunduly high.

In U.S. Pat. No. 5,159,027, disclosed is a polyphenylene ether resinhaving a specific cyclic end group which resin is available by meltkneading a polyphenylene ether having a specific end structure and acompound having functionality. While the number of Fries rearrangementstructures in the ordinarily employed polyphenylene ether is 0.18 orgreater per 100 recurring units of the resin, that in this polyphenyleneether resin can be reduced to 0.01 per 100 recurring units of the resin.It is reported that this resin has therefore excellent color tone.

The above-described technique however cannot produce a highly functionalpolyphenylene ether resin having Fries rearrangement structures reducedin the number to less than 0.01 per 100 recurring units.

In addition, Fries rearrangement can be suppressed only when thepolyphenylene ether has a specific cyclic end group so that theabove-described technique is not sufficient for obtaining a highlyfunctional polyphenylene ether resin.

As another technique for improving color tone/appearance, conventionallyemployed is addition of a plasticizer such as mineral oil to apolyphenylene ether, thereby lowering the processing temperature uponmelt extrusion. The resulting modified polyphenylene ether resin, whenmolded or formed, has improved color tone/appearance but hasdeteriorated heat resistance/mechanical physical properties.

Thus, modified polyphenylene ether resins available by the prior art donot satisfy the demand of industries, because they have drawbacks inequipment/energy or are not sufficient in the balance between colortone/appearance and heat resistance/mechanical physical properties.

The invention therefore relates to a modified polyphenylene ether resinand a preparation process thereof. An object of the present invention isto provide a modified polyphenylene ether resin which exhibitssufficient functionality, is free from problems in equipment or energy,assures well-balanced color tone/appearance and heatresistance/mechanical physical properties, and can satisfy the demand ofindustries sufficiently.

DISCLOSURE OF THE INVENTION

With a view to attaining the above-described object, the presentinventor has proceeded with an investigation and completed a modifiedpolyphenylene ether resin which is excellent from the viewpoints ofequipment and energy, has excellent color tone/appearance and moreover,has excellent heat resistance/mechanical physical properties; and apreparation process thereof.

In the present invention, there is thus provided a modifiedpolyphenylene ether resin which is a reaction product of 100 parts byweight of (A) a polyphenylene ether having a main chain structure of thefollowing formula (1):

wherein R₁ and R₄ each independently represents hydrogen, a primary orsecondary lower alkyl, a phenyl, an aminoalkyl or a hydrocarbonoxy andR₂ and R₃ each independently represents hydrogen, a primary or secondarylower alkyl or a phenyl), and 0.01 to 10.0 parts by weight of (3) amodifier selected from conjugated non-aromatic diene compounds,dienophilic compounds having one dienophile group and precursors of thediene or dienophilic compounds, wherein the number of a rearrangementstructure represented by the following formula (2):

(wherein R₁, R₂, R₃, and R₄ have the same meanings as defined above inthe formula (1)) is less than 0.01 per 100 phenylene ether units of theformula (1).

BEST MODE FOR CARRYING OUT THE INVENTION

The modified polyphenylene ether resin of the invention is a reactionproduct obtained by reacting 100 parts by weight of polyphenylene ether(A) with 0.01 to 10.0 parts by weight of modifier (B) selected fromconjugated non-aromatic diene compounds, dienophilic compounds havingone dienophile group and precursors of the diene or dienophiliccompounds; and has functionality.

The modified polyphenylene ether resin of the invention contains, per100 phenylene ether units of the formula (1), less than 0.01rearrangement structure which is represented by the formula (2) and isconsidered to cause coloring of the polyphenylene ether, and it is freeof thermal deterioration and discoloration and is excellent in colortone/appearance.

The modified polyphenylene ether resin of the invention containing, per100 phenylene ether units of the formula (1), less than 0.005rearrangement structure which is represented by the formula (2) and isconsidered to cause coloring of the polyphenylene ether is morepreferred.

In addition, the modified polyphenylene ether resin of the inventiondoes not contain a plasticizer so that it does not lose heat resistanceand mechanical physical properties which the polyphenylene etheroriginally has.

The modified polyphenylene ether resin of the invention therefore hassufficient functionality, is excellent in color tone/appearance, inoperation/energy, and in heat resistance/mechanical physical properties.

A molded or formed product available from the modified polyphenyleneether resin of the invention can be used widely for uses of a polymeralloy because of its sufficient functionality. In addition, since theproduct is free from drawbacks in operation/energy and is good in colortone/appearance and heat resistance/mechanical physical properties,products or parts of various industrial fields which can fully satisfythe demand of the industries can be provided.

Polyphenylene ether (A) of the invention is a plastic material which hasa main chain structure of the following formula (1):

(wherein R₁ and R₄ each independently represents hydrogen, a primary orsecondary lower alkyl, a phenyl, an aminoalkyl or a hydrocarbonoxy andR₂ and R₃ each independently represents hydrogen, a primary or secondarylower alkyl or a phenyl); is suited for the formation of products/partsof any shape by melt injection molding, melt extrusion or the likeforming or molding method, and is widely used as a material forproducts/parts in electric/electronic fields, automotive field andvarious other industrial fields.

Polyphenylene ether (A) of the invention is a polymer or copolymer whichhas a reduced viscosity, as measured at 30° C. using a chloroformsolution at a concentration of 0.5 g/dl, preferably ranging from 0.15 to1.0 dl/g, more preferably ranging from 0.20 to 0.70 dl/g.

Specific examples of polyphenylene ether (A) of the invention includepoly(2,6-dimethyl-1,4-phenylene ether),poly(2-methyl-6-ethyl-1,4-phenylene ether),poly(2-methyl-6-phenyl-1,4-phenylene ether) andpoly(2,6-dichloro-1,4-phenylene ether).

Further specific examples of polyphenylene ether (A) of the inventioninclude polyphenylene ether copolymers such as copolymer of2,6-dimethylphenol with another phenol (ex. 2,3,6-trimethylphenol or2-methyl-6-butylphenol).

Among the above-exemplified polyphenylene ethers (A) of the invention,poly(2,6-dimethyl-1,4-phenylene ether) and a copolymer of2,6-dimethylphenol and 2,3,6-trimethylphenol are preferred, withpoly(2,6-dimethyl-1,4-phenylene ether) being most preferred.

No particular limitation is imposed on the preparation process ofpolyphenylene ether (A) to be used in the invention.

Examples of the process for preparing polyphenylene ether (A) to be usedin the invention include that described in U.S. Pat. No. 3,306,874wherein oxidative polymerization of 2,6-xylenol is conducted in thepresence of a cuprous salt-amine complex as a catalyst.

Processes as described in U.S. Pat. Nos. 3,306,875, 3,257,357 and3,257,358, JP-B-52-17880, and JP-A-50-51197 and 63-152628 are alsopreferred as a process for preparing polyphenylene ether (A).

Polyphenylene ether (A) of the invention is preferred to have an endstructure represented by the following formula (3):

(wherein R₁, R₂, R₃, and R₄ have the same meanings as defined as R₁, R₂,R₃, and R₄ in the above-described formula (1)).

Polyphenylene ether (A) of the invention is more preferred to have anend structure represented by the following formula (4):

(wherein R₅ and R₅′ each represents hydrogen ox an alkyl).

One example of a process for obtaining polyphenylene ether (A) having anend structure of the formula (4) is to conduct oxidative coupling of2,6-dimethylphenol in the presence of a primary or secondary amine byusing a copper- or manganese-containing catalyst.

As the primary or secondary amine, dialkylamines are preferred, withdi-n-butylamine, dimethylamine and diethylamine being more preferred.

Polyphenylene ether (A) having an end structure of the formula (4)acquires high activity by passing through a quinone-methide endstructure of the formula (5):

To polyphenylene ether (A) of the invention, any additive may be addedaccording to the purpose.

Examples of the additive to be used for polyphenylene ether (A) of theinvention include heat stabilizer, antioxidant, UV absorber, surfactant,lubricant, filler, polymer additive, dialkyl peroxide, diacyl peroxide,peroxy, peroxycarbonate, hydroperoxide and peroxyketal.

Modifier (B) to be used in the invention is selected from conjugatednon-aromatic diene compounds, dienophilic compounds having onedienophile group and precursors for these diene or dienophiliccompounds.

Alternatively, modifier (B) to be used in the invention may be a mixtureof at least two selected from conjugated non-aromatic diene compounds,dienophilic compounds having one dienophile group and precursors forthese diene or dienophilic compounds.

Suitable examples of the conjugated non-aromatic diene compound to beused as modifier (B) in the invention include butadiene, cyclopentadieneand 1,3-cyclohexadiene.

The term “dienophilic compound having one dienophile hi group” as usedherein means an unsaturated compound which can be added to a diene inDiels-Alder reaction (for example, refer to “Advanced Organic Chemistry,pp. 206-211(1963)”, Fieser and Fieser, New York, 1963).

Suitable examples of the one-dienophile-containing dienophilic compoundto be used as modifier (B) in the invention include maleimide, N-alkylmaleimides, N-aryl maleimides, acenaphthylene, indene, cinnamaldehyde,N-alkylmaleinamic acids, N-arylmaleinamic acids, maleic anhydride,maleic acid, fumaric acid, phenyl maleimide, itaconic acid,naphthoquinone, 2-methyl-1,4-naphthoquinone, glycidyl methacrylate andglycidyl acrylate.

Suitable examples of the precursor for the diene or dienophiliccompounds to be used as modifier (B) in the invention includeacenaphthenol, methandic anhydride and malic acid.

Compounds having, in the molecule thereof, at least one of a doublebond, at least one carboxyl group, acyl oxide group, imino group, imidegroup, hydroxy group and glycidyl group are preferably employed asmodifier (B) of the invention.

Among them, maleic anhydride, maleic acid, fumaric acid, phenylmaleimide, itaconic acid, malic acid, glycidyl acrylate or glycidylmethacrylate are especially preferred as modifier (B) of the invention.

In a process for preparing the modified polyphenylene ether resin of theinvention, 100 parts by weight of polyphenylene ether (A) is mixed andreacted with 0.01 to 10.0 parts by weight of the above-describedmodified (B)

When the amount of modifier (B) is less than 0.01 part by weight, theamount of a functional group becomes insufficient.

When the amount of modifier (B) exceeds 10.0 parts by weight, on theother hand, a large amount of modifier (B) remains unreacted in themodified polyphenylene ether resin, causing silver streaks upon moldingof forming the resulting resin.

In the invention, mixing and reaction of 100 parts by weight ofpolyphenylene ether (A) with 0.1 to 5.0 parts by weight of modifier (B)are preferred.

Mixing and reaction of 100 parts by weight of polyphenylene ether (A)with 0.2 to 3.0 parts by weight of modifier (B) are more preferred.

The polyphenylene ether resin of the invention imparted withfunctionality can be imparted with functionality again by using acompound reactive therewith as a raw material.

The modified polyphenylene ether resin of the invention preferablycontains, in 5 g of it, not greater than 100 foreign substances having asize of at least 50 μm. The term “foreign substances” as used hereinmeans matters which are different in color (brown or dark brown) fromthe surroundings and insoluble in a solvent for the modifiedpolyphenylene ether.

The number of the foreign substances contained in 5 g of the modifiedpolyphenylene ether resin and having a size of at least 50 μm can bedetermined by dissolving 5 q of the modified polyphenylene ether in 50ml of chloroform, filtering the resulting solution through a filterpaper and then counting the number of the foreign substances having asize of at least 50 μm and left on the filter paper by visual ormicroscopic observation.

In the invention, a modified polyphenylene ether containing, in 5 gthereof, not greater than 50 foreign substances is preferred.

In the invention, a modified polyphenylene ether containing, in 5 gthereof, not greater than 10 foreign substances is markedly preferred.

In the invention, a modified polyphenylene ether containing, in 5 gthereof, not greater than 5 foreign substances is most preferred.

The modified polyphenylene ether resin of the sat invention ispreferably a reaction product of 100 parts by weight of polyphenyleneether (A) having a main chain structure of the formula (1) and at thesame time, having an end structure of the following formula (4):

(wherein R₅ and R₅′ each represents hydrogen or an alkyl) and 0.01 to10.0 parts by weight of modifier (B) selected from conjugatednon-aromatic diene compounds, dienophilic compounds having onedienophile group and precursors of the diene or dienophilic compounds.

Polyphenylene ether (A) having the end structure of the formula (4)acquires high activity after passing through a quinone-methide type endstructure of the following formula (5):

A Diels-Alder reaction occurs between this quinone-methide type endstructure and modifier (B), whereby available is the modifiedpolyphenylene ether resin having a structure preferred in the invention,that is, a cyclic end structure of the following formula (6):

(in the formula (6), R₁, R₂ and R₃ have the same meanings as defined inthe formula (1), and R₇, R₈, R₉ and R₁₀ are each determined by theresults of the Diels-Alder reaction of polyphenylene ether (A) having astructure of the formula (5) and modifier (B) and differs with the kindof modifier (B), or R₇, R₈, R₉ and R₁₀ may each represent a spirocyclicstructure independently bonded thereto).

The reaction of polyphenylene ether (A) with modifier (B) happens toprepare a modified polyphenylene ether resin having a modified structureof formula (8) below, which is considered to result from the reaction ofmodifier (B) and a radical intermediate structure of the followingformula (7):

(in the formula (7), R₁, R₂, R₃ and R₄ have the same meanings as definedin the formula (1) and R₁₁ represents hydrogen or a polymer having aphenylene ether unit)

(in the formula (8), R₁, R₂, R₃ and R₁₁ have the same meanings asdefined in the formula (7), or R₇, R₈, R₉ and R₁₀ in the formula (8) areeach determined by the results of radical reaction of polyphenyleneether (A) having a structure of the formula (7) and modifier (By anddiffers with the kind of modifier (B), or R7, R₈R₉ and R₁₀ may eachrepresent a spirocyclic structure independently bonded thereto).

The modified structure of the formula (8) has high functionality buteffects for improving color tone and the number of foreign substancesupon secondary processing of the modified polyphenylene ether resin arenot superior to those of the cyclic end structure of the formula (6).

In the present invention, preferably employed is the modifiedpolyphenylene ether resin containing, per 100 phenylene ether units ofthe following formula (1):

(wherein R₁ and R₄ each independently represents hydrogen, a primary orsecondary lower alkyl, a phenyl, an aminoalkyl or a hydrocarbonoxy andR₂ and R₃ each independently represents hydrogen, a primary or secondarylower alkyl or a phenyl), Nc pieces, on average, of the cyclic modifiedstructure of the following formula (6):

(in the formula (6), R₁, R₂ and R₃ have the same meanings as defined inthe formula (1), and R₇, R₈, R₉and R₁₀ are each determined by theresults of the Diels-Alder reaction of polyphenylene ether (A) having astructure of the above-described formula (5) and modifier (B) anddiffers with the kind of modifier (E), or R₇, R₈, R₉ and R₁₀ may eachrepresent a spirocyclic structure independently bonded thereto) and Nopieces, on average, of the noncyclic modified structure of the followingformula (8):

(in the formula (8), R₁, R₂, R₃ and R₁₁ have the same meanings asdefined in the formula (7), or R₇, R₈, R₉ and R₁₀ in the formula (8) areeach determined by the results of radical reaction of polyphenyleneether (A) having a structure of the above-described formula (7) andmodifier (B) and differs with the kind of modifier (B), or R₇, R₈, R₉and R₁₀ may each represent a spirocyclic structure independently bondedthereto) at an Nc/No ratio of 1 or greater, because it is particularlysuperior in color tone and contains foreign substances in a markedlysmall amount.

In the invention, the modified polyphenylene ether resin having theNc/No ratio of 2 or greater is more preferably employed.

In the invention, the modified polyphenylene ether resin having theNc/No ratio of 3 or greater is especially preferably employed.

In the invention, the modified polyphenylene ether resin having amelting point of 150 to 260° C. and being in the form of powder havingan average particle size of 3.0 μm to 1.0 mm is preferably employed.

In the preparation process of the modified polyphenylene ether resin ofthe invention, the reaction temperature is not lower than a roomtemperature and not higher than the melting point of polyphenylene ether(A).

The term “room temperature” as used herein means 27° C.

In the invention, when the reaction temperature is less than the roomtemperature, polyphenylene ether (A) cannot react with modifier (B)sufficiently.

In the invention, crystalline polyphenylene ether having a melting pointis preferably employed as a raw material for polyphenylene ether (A).

Examples of the literature describing the relation between crystallinepolyphenylene ether and its melting point include “Journal of PolymerScience, Part A-2(6), 1141-1148(1968)”, “European Polymer Journal (9),293-300(1973)” and “Polymer, (19), 81-84(1978)”.

In the invention, the melting point of polyphenylene ether (A) isdefined as a peak top temperature of the peak observed in atemperature-heat flow rate graph availability increasing the temperatureof (A) at 20° C./min in measurement by differential scanning calorimeter(DSC).

In the invention, when there exist plural peak top temperatures, themelting point of polyphenylene ether (A) is defined by the highesttemperature among them.

In the preparation process of the modified polyphenylene ether resin inthe invention, preferred is polyphenylene ether (A) in the powdery formavailable by precipitation from a solution and having a melting point of150 to 260° C.

The polyphenylene ether sometimes contains therein a trace of a goodsolvent to be used in its polymerization step.

Examples of the good solvent for the polyphenylene ether includetoluene, o-xylene, m-xylene, p-xylene, ethylbenzene and chloroform.Although in the present invention, reaction of the polyphenylene etheris effected in the solid form and positive addition of a good solvent isnot required, the good solvent, which was used in the polymerizationstep, does not do any harm even if it is contained in the polymer in atrace. This case can be regarded as substantially solventless.

This “substantially solventless” state means that polyphenylene ether(A) remains as a substantially solid any the melting point ofpolyphenylene ether (A) appears clearly.

In the invention, polyphenylene ether (A) in the substantiallysolventless state preferably has a melting point of 150 to 260° C., morepreferably 200 to 260° C., especially 240 to 260° C.

Reaction under the substantially solventless state is especiallypreferred, because it does not need separating operation of a solvent,which makes this invention excellent from the viewpoints ofoperation/energy.

The above-described polyphenylene ether in the powdery form preferablyhas a heat of fusion (ΔH), available from the peak at DSC measurement,of 2 J/g or greater.

In the invention, at the reaction temperature exceeding the meltingpoint of polyphenylene ether (A), polyphenylene ether (A) is melted andsticks to the reactor employed.

At this time, when reaction of polyphenylene ether (A) and modifier (B)is promoted by intensive kneading, polyphenylene ether (A) hasdeteriorated color tone/appearance owing to the heat generated uponkneading.

In the invention, reaction temperature ranging from 100 to 230° C. ispreferred, with a range of 150 to 200° C. being especially preferred.

In the invention, the pressure upon reaction of polyphenylene ether (A)and modifier (B) preferably ranges from 0 to 2 MPa, with a range of 0 to1 MPa being especially preferred.

In the preparation process of the modified polyphenylene ether resin ofthe invention, use of a paddle drier as a reactor is preferred.

The modified polyphenylene ether resin of the invention can be preparedefficiently by using a paddle drier having a jacket set at a desiredtemperature.

In the preparation process of the modified polyphenylene ether resin ofthe invention, use of a Henschel mixer as a reactor is more preferred.

Use of a Henschel mixer as a reactor makes it possible to efficientlymix polyphenylene ether (A) and modifier (B) and heat the mixture byshearing heat, thereby preparing the modified polyphenylene ether resinof the invention efficiently.

As a preparation process of the modified polyphenylene ether resin ofthe invention, it is especially preferred to mix polyphenylene ether (A)and modifier (B) in advance by a paddle drier having a jacket set at adesired temperature and/or a Henschel mixer, heat the mixture and thencontinue reaction in a hopper.

There is, however, no particular limitation imposed on the preparationprocess of the modified polyphenylene ether resin of the invention.

The modified polyphenylene ether resin of the invention can be preparedby adding a reaction assistant.

Preferred examples of the reaction assistant used for the preparation ofthe modified polyphenylene ether resin of the invention include radicalinitiators, bases, inorganic acids, organic acids, inorganic acid saltsand organic acid salts.

The modified polyphenylene ether resin of the invention is excellent incolor tone/appearance.

The modified polyphenylene ether resin of the invention has excellentmechanical physical properties so that it can be used as it is.

The modified polyphenylene ether resin of the invention is preferablyused in the form of a polymer alloy or polymer composite obtained bymixing with another composition and then kneading in a molten state.

The modified polyphenylene ether resin of the invention is morepreferably used in the form of a polymer alloy or polymer compositeobtained by mixing the resin with another composition and a solvent anddissolving the former two in the latter.

The modified polyphenylene ether resin of the invention is especiallypreferred in the form of a polymer alloy kneaded with a polyamide,polyimide, polyether imide, polyester or polycarbonate.

No particular limitation is imposed on the use of the modifiedpolyphenylene ether resin of the invention and it can be used widely forelectric/electronic fields, automotive fields, various other industrialmaterial fields and food/package fields.

The polymer alloy or polymer composite containing the modifiedpolyphenylene ether resin of the invention can be preferably used inelectric/electronic fields, automotive fields, various other industrialmaterial fields, and food/package fields.

The polymer alloy obtained by kneading, in a molten state, the modifiedpolyphenylene ether resin of the invention with a polyamide, polyimideor polyester can be very preferably used in electric/electronic fields,automotive fields, various other industrial material fields, andfood/package fields, because of excellence in color tone/appearance,mechanical properties and productivity.

The modes for carrying out the invention will be illustrated in greaterdetail with reference to the following Examples, but the inventionshould not be construed as being limited thereto.

In Examples and Comparative Examples, the following polyphenylene ethers(A) were employed.

A-1: poly(2,6-dimethyl-1,4-phenylene ether) having a reduced viscosityof 0.54, which was obtained by oxidative polymerization of2,6-dimethylphenol.

A-2: poly(2,6-dimethyl-1,4-phenylene ether) having a reduced viscosityof 0.31, which was obtained by oxidative polymerization of2,6-dimethylphenol.

In Examples and Comparative Examples, the following modifiers (B) wereemployed.

B-1: maleic anhydride

B-2: fumaric acid

B-3: phenyl maleimide

B-4: maleic acid

B-5: glycidyl methacrylate

In Examples and Comparative Examples, the melting point was evaluated inthe following manner.

The peak top temperature in the temperature-heat flow rate graphavailable by heating polyphenylene ether (A) at 20° C./min using adifferential scanning calorimeter (DSC) was designated as its meltingpoint.

The temperature-heat flow rate graph of polyphenylene ether (A-1)exhibited a single peak. The melting point was 250° C., while the heatof melting ΔH was 20 J/g.

The temperature-heat flow rate graph of polyphenylene ether (A-2)exhibited a single peak. The melting point was 245° C., while the heatof melting ΔH was 22 J/g.

The average particle sizes of polyphenylene ethers (A-1) and (A-2) weremeasured, resulting in 50 μm and 25 μm, respectively.

EXAMPLE 1

In an autoclave equipped with a gas inlet were charged 100 g ofpolyphenylene ether (A-1), 2 g of modifier (B-1) and 5 iron balls forstirring having a diameter of 5 mm.

After the pressure inside of the autoclave was reduced to 10 mmHgthrough the gas inlet at room temperature, nitrogen of atmosphericpressure was introduced to purge the inside with nitrogen.

The above-described operation was repeated three times. The autoclavewas then hermetically sealed.

Upon pressure reduction and nitrogen purging, (A-1) and (B-1) releasedoutside of the system were collected.

The amounts of (A-1) and (B-1) released outside were 0.1 g and 0.02 g,respectively.

The hermetically sealed autoclave was placed in an oil bath set at 200°C., followed by vigorous shaking for 15 minutes.

The autoclave was then taken out from the oil bath and allowed to standat room temperature for 1 hour.

The autoclave was opened and Contents (C-1-1) in the powdery form wereharvested.

It was found that no molten substance was mixed in Contents (C-1-1).

The mass of Contents (C-1-1) was 101.7 g.

A 50 g portion of Contents (C-1-1). was washed with 100 ml of acetone,followed by filtration through a glass filter.

This operation was repeated 5 times, whereby Wash 1 (D-1-1) and Filtrate1 (E-1-1) were obtained.

Analysis of the gas chromatogram revealed that 0.3 g of modifier (B) wascontained in Filtrate 1 (E-1-1).

A 20 g portion of Dried substance 1 (F-1-1) obtained by drying Wash 1(D-1-1) was washed with 40 ml of acetone, followed by filtration througha glass filter.

This operation was repeated 5 times, whereby Wash 2 (H-1-1) and Filtrate2 (G-1-1) were obtained.

Analysis of the gas chromatogram revealed that Filtrate 2 (G-1-1) wasfree of modifier (B-1).

Dried substance 1 (F-1-1) was sandwiched between sheets eachsuccessively composed of a polytetrafluoroethylene sheet, an aluminumsheet and an iron sheet, with the polytetrafluoroethylene sheet beingdisposed on the side of Dried substance 1. The laminate thus formed wascompression molded at 10 MPa by using a pressing machine set at 280° C.,whereby Film (I-1-1) was obtained.

By a similar operation, Film (A-1-1) was obtained from polyphenyleneether (A-1).

The resulting Films (I-1-1) and (A-1-1) were each subjected to infraredspectroscopic measurement using a Fourier transform infraredspectrometer (“IR-420 Type”, trade name; manufactured by JASCOCorporation).

As a result of measurement of (I-1-1), a peak derived from maleic acidadded to the polyphenylene ether was observed at 1790 cm⁻¹.

As a result of measurement of (A-1-1), on the other hand, no peak wasobserved at 1790 cm⁻¹.

In addition, ¹H-NMR measurement was conducted on each of the solutionsof Dried product 1 (F-1-1), Film (I-1-1) and Film (A-1-1) in deuteratedchloroform by using a Fourier transform NMR analyzer “Lambda 400” (tradename; manufactured by Nippon Denshisha).

From Dried product 1 (F-1-1), no peak was recognized at 6.92 ppm derivedfrom ¹H at the 3,5-position of the benzene ring of the following formula(9).

From Film (I-1-1), a peak at 6.92 ppm derived from ¹H at the3,5-position of the benzene ring derived from the rearrangementstructure represented by the formula (9) was recognized. Based on thecomparison in area between this peak and the peak at 6.43 ppm derivedfrom ¹H at the 3,5-position of the main-chain benzene ring representedby the formula (10), the number of the rearrangement structure of theformula (9) was analyzed to be 0.004 per 100 main chain structures ofthe formula (10).

With regards to (A-1-1), a large peak at 6.92 ppm derived from ¹H at the3,5-position of the benzene ring derived from the rearrangementstructure represented by the formula (9) was confirmed, resulting inanalysis that the number of the rearrangement structure of the formula(9) was 0.11 per 100 main chain structures of the formula (10).

NMR measurement results indicate that a ratio Nc/No of the number (Nc)of the structure of the following formula (11):

to the number (No) of the structure of the following formula (12):

was 2.5.

By using a pressing machine set at a mold temperature of 280° C., 20 gof Dried product 1 (F-1-1) was press molded, whereby Flat-plate molding(J-1-1) of 50×80×3 mm in size was obtained.

The resulting flat-plate molding was transparent and pale yellow and noforeign substances were observed from it.

EXAMPLE 2

100 g of polyphenylene ether (A-2) and 2 g of modifier (B-2) werecharged in an autoclave, followed by purging with nitrogen andhermetical sealing in a similar manner to Example 1.

The amounts of (A-2) and (B-2) released out of the system upon pressurereduction and nitrogen purging were 0.06 g and 0.02 g, respectively.

In a similar manner to Example 1, the hermetically sealed autoclave wasplaced in an oil bath set at 200° C., followed by vigorous shaking for 5minutes, whereby 101.6 g of Contents (C-2-1) were obtained in thepowdery form.

From a 50 g portion of Contents (C-2-1), Wash 1 (D-2-1), Filtrate 1(E-2-1), 49.4 g of Dried substance 1 (F-2-1) and Filtrate 2 (G-2-1) wereobtained in a similar manner to Example 1.

The amounts of modifier (B-2) contained in Filtrate 1 (E-2-1) andFiltrate 2 (G-2-1) were 0.3 g and 0 g, respectively.

In a similar manner to Example 1, Film (I-2-1) was obtained from Driedsubstance 1 (F-2-1).

By infrared spectroscopic measurement of (I-2-1), a peak derived fromfumaric acid added to the polyphenylene ether was observed at 1788 cm⁻¹.

In a similar manner to Example 1, Flat-plate molding (J-2-1) wasobtained.

The resulting flat-plate molding was, as that obtained in Example 1,transparent and pale yellow and no foreign substances were observed fromit.

In a similar manner to Example 1, ¹H-NMR measurement of Dried Substance1 (F-2-1) and Film (I-2-1) was conducted.

Analysis based on the comparison in area between the peak at 6.92 ppmand the peak at 6.43 ppm revealed that the number of the rearrangementstructures of the formula (9) per 100 main chain structures of theformula (10) was 0 in Dried Product (F-2-1) and 0.003 in Film (I-2-1).

EXAMPLE 3

100 g of polyphenylene ether (A-1) and 2 g of modifier (B-1) werecharged in an autoclave, followed by purging with nitrogen andhermetical sealing in a similar manner to Example 1.

The amounts of (A-1) and (B-1) released out of the system upon pressurereduction and nitrogen purging were 0.08 g and 0.03 g, respectively.

The hermetically sealed autoclave was placed in an oil bath set at 150°C., followed by shaking for 5 minutes, whereby 101.0 g of Contents(C-3-1) were obtained in the powdery form.

From a 50 g portion of Contents (C-3-1), Wash 1 (D-3-1), Filtrate 1(E-3-1), 49.0 g of Dried substance 1 (F-3-1) and Filtrate 2 (G-3-1) wereobtained in a similar manner to Example 1.

The amounts of modifier (B-1) contained in Filtrate 1 (E-3-1) andFiltrate 2 (G-3-1) were 0.4 g and 0 g, respectively.

In a similar manner to Example 1, Film (I-3-1) was obtained from Driedsubstance 1 (F-3-1).

By infrared spectroscopic measurement of (I-3-1), a peak derived frommaleic anhydride added to the polyphenylene ether was observed at 1790cm⁻¹.

In a similar manner to Example 1, Flat-plate molding (J-3-1) which wastransparent and pale yellow and from which no foreign substances wereobserved was obtained.

¹H-NMR measurement and analysis in a similar manner to Example 1revealed that the number of the rearrangement structures of the formula(9) per 100 main chain structures of the formula (10) was 0 in DriedProduct (F-3-1) and 0.004 in Film (I-3-1).

EXAMPLE 4

100 g of polyphenylene ether (A-1) and 2 g of modifier (B-1) werecharged in an autoclave, followed by purging with nitrogen andhermetical sealing in a similar manner to Example 1.

The amounts of (A-1) and (B-1) released out of the system upon pressurereduction and nitrogen purging were 0.1 g and 0.03 g, respectively.

The hermetically sealed autoclave was placed in an oil bath set at 130°C., followed by shaking for 5 minutes, whereby 101.2 g of Contents(C-4-1) were obtained in the powdery form.

From a 50 g portion of Contents (C-4-1), Wash 1 (D-4-1), Filtrate 1(E-4-1), 49.0 g of Dried substance 1 (F-4-1) and Filtrate 2 (G-4-1) wereobtained in a similar manner to Example 1.

The amounts of modifier (B-1) contained in Filtrate 1 (E-4-1) andFiltrate 2 (G-4-1) were 0.3 g and 0 g, respectively.

In a similar manner to Example 1, Film (I-4-1) was obtained from Driedsubstance 1 (F-4-1).

By infrared spectroscopic analysis of (I-4-1), a peak derived frommaleic anhydride added to the polyphenylene ether was observed at 1789cm⁻¹.

In a similar manner to Example 1, Flat-plate molding (J-4-1) which wastransparent and pale yellow and from which no foreign substances wereobserved was obtained.

¹H-NMR measurement and analysis in a similar manner to Example 1revealed that the number of the rearrangement structures of the formula(9) per 100 main chain structures of the formula (10) was 0 in DriedProduct (F-4-1) and 0.003 in Film (I-4-1).

EXAMPLE 5

100 g of polyphenylene ether (A-1) and 2 g of modifier (B-1) werecharged in an autoclave, followed by purging with nitrogen andhermetical sealing in a similar manner to Example 1.

The amounts of (A-1) and (B-1) released out of the system upon pressurereduction and nitrogen purging were 0.1 g and 0.05 g, respectively.

The hermetically sealed autoclave was placed in an oil bath set at 215°C., followed by shaking for 5 minutes, whereby 100.0 g of Contents(C-5-1) were obtained in the powdery form.

From a 50 g portion of Contents (C-5-1), Wash 1 (D-5-1), Filtrate 1(E-5-1), 49.3 g of Dried substance 1 (F-5-1) and Filtrate 2 (G-5-1) wereobtained in a similar manner to Example 1.

The amounts of modifier (B-1) contained in Filtrate 1 (E-5-1) andFiltrate 2 (G-5-1) were 0.3 g and 0 g, respectively.

In a similar manner to Example 1, Film (I-5-1) was obtained from Driedsubstance 1 (F-5-1).

By infrared spectroscopic measurement of (I-5-1), a peak derived frommaleic anhydride added to the polyphenylene ether was observed at 1790cm⁻¹.

In a similar manner to Example 1, Flat-plate molding (J-5-1) which wastransparent and pale yellow and from which no foreign substances wereobserved was obtained.

¹H-NMR measurement and analysis in a similar manner to Example 1revealed that the number of the rearrangement structures of the formula(9) per 100 main chain structures of the formula (10) was 0.001in DriedProduct (F-5-1) and 0.006 in Film (I-5-1).

EXAMPLE 6

100 g of polyphenylene ether (A-1) and 2 g of modifier (B-1) werecharged in an autoclave, followed by purging with nitrogen andhermetical sealing in a similar manner to Example 1.

The amounts of (A-1) and (B-1) released out of the system upon pressurereduction and nitrogen purging were 0.17 g and 0.05 g, respectively.

The hermetically sealed autoclave was placed in an oil bath set at 225°C., followed by shaking for 5 minutes, whereby 99.0 g of Contents(C-6-1) were obtained in the form of slightly agglomerated powder.

From a 50 g portion of Contents (C-6-1), Wash 1 (D-6-1), Filtrate 1(E-6-1), 49.5 g of Dried substance 1 (F-6-1) and Filtrate 2 (G-6-1) wereobtained in a similar manner to Example 1.

The amounts of modifier (B-1) contained in Filtrate 1 (E-6-1) andFiltrate 2 (G-6-1) were 0.1 g and 0 g, respectively.

In a similar manner to Example 1, Film (I-6-1) was obtained from Driedsubstance 1 (F-6-l).

By infrared spectroscopic measurement of (I-6-1), a peak derived frommaleic anhydride added to the polyphenylene ether was observed at 1790cm⁻¹.

In a similar manner to Example 1, Flat-plate molding (J-6-1) which wastransparent and pale yellow and from which no foreign substances wereobserved was obtained.

¹H-NMR measurement and analysis in a similar manner to Example 1revealed that the number of the rearrangement structures of the formula(9) per 100 main chain structures of the formula (10) was 0.004 in DriedProduct (F-6-1) and 0.008 in Film (I-6-1).

COMPARATIVE EXAMPLE 1

100 g of polyphenylene ether (A-1) and 2 g of modifier (B-1) werecharged in an autoclave, followed by purging with nitrogen andhermetical sealing in a similar manner to Example 1.

The amounts of (A-1) and (B-1) released out of the system upon pressurereduction and nitrogen purging were 0.1 g and 0.05 g, respectively.

The hermetically sealed autoclave was placed in an oil bath set at 260°C., followed by shaking for 5 minutes, whereby Contents (C-7-1) wereobtained.

It was difficult to take out Contents (C-7-1) from the autoclave becauseit stuck to the inside thereof.

From a 50 g portion of Contents (C-7-1), Wash 1 (D-7-1), Filtrate 1(E-7-1), 49.6 g of Dried substance 1 (F-7-1) and Filtrate 2 (G-7-1) wereobtained in a similar manner to Example 1.

The amounts of modifier (B-1) contained in Filtrate 1 (E-7-1) andFiltrate 2 (G-7-1) were 0.2 g and 0 g, respectively.

In a similar manner to Example 1, Film (I-7-1) was obtained.

By infrared spectroscopic measurement of (I-7-1), a peak derived frommaleic anhydride added to the polyphenylene ether was observed at 1790cm⁻¹.

Flat-plate molding (O-7-1) which was transparent and dark yellow andfrom which no foreign substances were observed was obtained.

¹H-NMR measurement and analysis in a similar manner to Example 1revealed that the number of the rearrangement structures of the formula(9) per 100 main chain structures of the formula (10) was 0.012 in DriedProduct (F-7-1) and 0.02 in Film (I-7-1).

COMPARATIVE EXAMPLE 2

In a Henschel mixer, 5 kg of polyphenylene ether (A-1) and 100 g ofmodifier (B-1) were mixed. An attempt was made on extrusion kneading ofthe resulting mixture using an extruder (“ZSK-25 Type”, trade name;manufactured by Werner & Pfleiderer) having a barrel temperature set at340° C.

From the pellets thus obtained, a film was prepared in a similar mannerto Example 1. As a result of infrared spectroscopic measurement of thefilm, a peak derived from maleic anhydride added to the polyphenyleneether was observed at 1790 cm⁻¹.

Flat-plate molding obtained in a similar manner to Example 1 was foundto be dark brown and contain black foreign substances.

¹H-NMR measurement and analysis in a similar manner to Example 1revealed that the number of the rearrangement structures of the formula(9) per 100 main chain structures of the formula (10) was 0.03 in thepellets and 0.05 in the flat-plate molding.

EXAMPLE 7

100 g of polyphenylene ether (A-1) and 0.3 g of modifier (B-1) werecharged in an autoclave, followed by purging with nitrogen andhermetical sealing in a similar manner to Example 1.

The amounts of (A-1) and (B-1) released out of the system upon pressurereduction and nitrogen purging were 0.1 g and 0.01 g, respectively.

The hermetically sealed autoclave was placed in an oil bath set at 200°C., followed by shaking for 5 minutes, whereby 100.1 g of Contents(C-8-1) were obtained in the powdery form.

From a 50 g portion of Contents (C-8-1), Wash 1 (D-8-1), Filtrate 1(E-8-1), 49.8 g of Dried substance 1 (F-8-1) and Filtrate 2 (G-8-1) wereobtained in a similar manner to Example 1.

The amounts of modifier (B-1) contained in Filtrate 1 (E-8-1) andFiltrate 2 (G-8-1) were 0.05 g and 0 g, respectively.

In a similar manner to Example 1, Film (I-8-1) was obtained.

By infrared spectroscopic measurement of (I-8-1), a peak derived frommaleic anhydride added to the polyphenylene ether was observed at 1790cm⁻¹.

In a similar manner to Example 1, Flat-plate molding (J-8-1) which wastransparent and pale yellow and from which no foreign substances wereobserved was obtained.

-   -   ¹H-NMR measurement and analysis in a similar manner to Example 1        revealed that the number of the rearrangement structures of the        formula (9) per 100 main chain structures of the formula (10)        was 0 in Dried Product (F-8-1) and 0.003 in Film (I-8-1).

COMPARATIVE EXAMPLE 3

100 g of polyphenylene ether (A-1) and 0.05 g of modifier (B-1) werecharged in an autoclave, followed by purging with nitrogen andhermetical sealing in a similar manner to Example 1.

The amounts of (A-1) and (B-1) released out of the system upon pressurereduction and nitrogen purging were 0.2 g and 0.01 g, respectively.

The hermetically sealed autoclave was placed in an oil bath set at 200°C., followed by shaking for 5 minutes, whereby 100 g of Contents (C-9-1)were obtained in the fat powdery form.

From a 50 g portion of Contents (C-9-1), Wash 1 (D-9-1), Filtrate 1(E-9-1), 49.7 g of Dried substance 1 (F-9-1) and Filtrate 2 (G-9-1) wereobtained in a similar manner to Example 1.

The amounts of modifier (B-1) contained in Filtrate 1 (E-9-1) andFiltrate 2 (G-9-1) were 0.006 g and 0 g, respectively.

In a similar manner to Example 1, Film (I-9-1) was obtained.

By infrared spectroscopic measurement of (I-9-1), a peak at 1790 cm⁻¹derived from maleic anhydride was not observed clearly.

EXAMPLE 8

100 g of polyphenylene ether (A-1) and 9 g of modifier (B-1) werecharged in an autoclave, followed by purging with nitrogen andhermetical sealing in a similar manner to Example 1.

The amounts of (A-1) and (B-1) released out of the system upon pressurereduction and nitrogen purging were 0.2 g and 0.8 g, respectively.

The hermetically sealed autoclave was placed in an oil bath set at 200°C., followed by shaking for 5 minutes, whereby 106.5 g of Contents(C-10-1) were obtained in the powder form.

From a 50 g portion of Contents (C-10-1), Wash 1 (D-10-1), Filtrate 1(E-10-1), 45.7 g of Dried substance 1 (F-10-1) and Filtrate 2 (G-10-1)were obtained in a similar manner to Example 1.

The amounts of modifier (B-1) contained in Filtrate 1 (E-1₀-1) andFiltrate 2 (G-10-1) were 4.0 g and 0 g, respectively.

In a similar manner to Example 1, Film (I-10-1) was obtained.

By infrared spectroscopic measurement of (I-10-1), a peak derived frommaleic anhydride added to the polyphenylene ether was observed at 1790cm⁻¹.

In a similar manner to Example 1, Flat-plate molding (J-10-1) which wastransparent and pale yellow and from which no foreign substances wereobserved was obtained.

¹H-NMR measurement and analysis in a similar manner to Example 1revealed that the number of the rearrangement structures of the formula(9) per 100 main chain structures of the formula (10) was 0 in DriedProduct (F-10-1) and 0.004 in Film (I-10-1).

COMPARATIVE EXAMPLE 4

100 g of polyphenylene ether (A-1) and 12 g of modifier (B-1) werecharged in an autoclave, followed by purging with nitrogen andhermetical sealing in a similar manner to Example 1. The amounts of(A-1) and (B-1) released out of the system upon pressure reduction andnitrogen purging were 0.5 g and 2.8 g, respectively.

The hermetically sealed autoclave was placed in an oil bath set at 200°C., followed by shaking for 5 minutes, whereby 100.5 g of Contents(C-11-1) were obtained in the mass form. It was difficult to take it outfrom the autoclave because it was in the mass form.

From a 50 g portion of Contents (C-11-1), Wash 1 (D-11-1), Filtrate 1(E-11-1), 43.7 g of Dried substance 1 (F-1-1) and Filtrate 2 (G-71-1)were obtained in a similar manner to Example 1.

The amounts of modifier (B-1) contained in Filtrate 1 (E-11-1) andFiltrate 2 (G-11-1) were 5.3 g and 0 g, respectively.

In a similar manner to Example 1, Film (I-11-1) was obtained.

By infrared spectroscopic measurement of (I-11-1), a peak at 1790 cm⁻¹derived from maleic anhydride was observed.

In a similar manner to Example 1, Flat-plate molding (J-11-1) which wastransparent and pale yellow and from which no foreign substances wereobserved was obtained.

EXAMPLE 9

In a paddle drier manufactured by Nara Machinery Co., Ltd. were charged10 kg of polyphenylene ether (A-1) and 200 g of modifier (B-1), followedby nitrogen purging while stirring inside of the drier.

After nitrogen purging, the paddle drier was hermetically sealed. Whileinternally stirring, the jacket temperature was increased from roomtemperature to 180° C. over 1 hour.

After keeping the temperature at 180° C. for 1 hour, the jackettemperature was lowered to room temperature over 1 hour.

As a result, 9.85 kg of Contents (C-12-1) were obtained in the powderyform.

From a 50 g portion of Contents (C-12-1), Wash 1 (D-12-1), Filtrate 1(E-12-1), 49.2 g of Dried substance 1 (F-12-1) and Filtrate 2 (G-12-1)were obtained in a similar manner to Example 1.

The amounts of modifier (B-1) contained in Filtrate 1 (E-12-1) andFiltrate 2 (G-12-1) were 0.2 g and 0 g, respectively.

In a similar manner to Example 1, Film (I-12-1) was obtained.

By infrared spectroscopic measurement of (I-12-1), a peak derived frommaleic anhydride added to the polyphenylene ether was observed at 1790cm⁻¹. In a similar manner to Example 1, Flat-plate molding (J-12-1)which was transparent and pale yellow and from which no A foreignsubstances were observed was obtained.

¹H-NMR measurement and analysis in a similar manner to Example 1revealed that the number of the rearrangement structures of the formula(9) per 100 main chain structures of the formula (10) was 0.001 in DriedProduct (F-12-1) and 0.004 in Film (I-12-1).

In a Henschel mixer, a 1 kg portion of Contents (C-12-1), 1 kg of (A-1),1.6 kg of a polyamide 6,6 resin (“Leona Resin 1300S”, trade name;product of Asahi Kasei Corporation) and 0.4 kg of a hydrogenated SBblock copolymer (“Tuftec H1077”, trade name; product of Asahi KaseiCorporation) were mixed, followed by extrusion kneading by using anextruder (“Model ZSK-25”, trade name; manufactured by Werner &Pfleiderer) having a barrel temperature set at 340° C., whereby Pellets(P-12-1) were obtained.

Pellets (P-12-1) were injection molded by an injection molder into anASTM standard test piece. Its tensile strength (ASTM D-638, 230° C.),tensile elongation at break (ASTM D-638, 23° C.) and Izod (notched)impact strength (ASTM D-256, 23° C.) were measured in accordance withthe ASTM standards.

Measurement revealed that the tensile strength was 61 MPa, tensileelongation at break was 100% or greater and Izod (notched) impactstrength was 500 J/m.

COMPARATIVE EXAMPLE 5

In a similar manner to Example 9, 2 kg of (A-1), 1.6 kg of a polyamide6,6 resin (“Leona Resin 1300S”, trade name; product of Asahi KaseiCorporation) and 0.4 kg of a hydrogenated SB block copolymer (“TuftecH1077”, trade name; product of Asahi Kasei Corporation) were mixed in aHenschel mixer, followed by extrusion kneading by using an extruder(“Model ZSK-25”, trade name; manufactured by Werner & Pfleiderer) havinga barrel temperature set at 340° C., whereby Pellets (P-13-1) wereobtained. Pellets (P-13-1) were injection molded by an injection molderinto an ASTM standard test piece. Its tensile strength (ASTM D-638, 23°C.), tensile elongation at break (ASTM D-638, 23° C.) and Izod (notched)impact strength IASTM D-256, 23° C.) were measured in accordance withthe ASTM standards.

Measurement revealed that the tensile strength was 57 MPa, tensileelongation at break was 5% and Izod (notched) impact strength was 27J/m.

EXAMPLE 10

100 g of polyphenylene ether (A-1) and 2 g of modifier (B-3) werecharged in an autoclave, followed by purging with nitrogen andhermetical sealing in a similar manner to Example 1.

The amounts of (A-1) and (B-3) released out of system upon pressurereduction and nitrogen purging were 0.2 g and 0.8 g, respectively.

The hermetically sealed autoclave was placed in an oil bath set at 200°C., followed by shaking for 5 minutes, whereby 100.5 g of Contents(C-14-1) were obtained in the powdery form.

From a 50 g portion of Contents (C-14-1), Wash 1 (D-14-1), Filtrate 1(E-14-1), 48.9 g of Dried substance 1 (F-14-1) and Filtrate 2 (G-14-1)were obtained in a similar manner to Example 1.

The amounts of modifier (B-3) contained in Filtrate 1 (E-14-1) andFiltrate 2 (G-14-1) were 0.5 g and 0 g, respectively.

In a similar manner to Example 1, Flat-plate molding (J-14-1) which wastransparent and pale yellow and from which no foreign substances wereobserved was obtained.

¹H-NMR measurement and analysis in a similar manner to Example 1revealed that the number of the rearrangement structures of the formula(9) per 100 main chain structures of the formula (10) was 0 in DriedProduct (F-14-1) and 0.002 in Film (I-14-1).

EXAMPLE 11

100 g of polyphenylene ether (A-1) and 2 g of modifier (B-4) werecharged in an autoclave, followed by nitrogen purging and hermeticalsealing in a similar manner to Example 1.

The amounts of (A-1) and (B-4) released out of the system upon pressurereduction and nitrogen purging were 0.2 g and 0.6 g, respectively.

The hermetically sealed autoclave was placed in an oil bath set at 200°C., followed by shaking for 5 minutes, whereby 100.2 g of Contents(C-15-1) were obtained in the powdery form.

From a 50 g portion of Contents (C-15-1), Wash 1 (D-15-1), Filtrate 1(E-15-1), 49.2 g of Dried substance 1 (F-15-1) and Filtrate 2 (G-15-1)were obtained in a similar manner to Example 1.

The amounts of modifier (B-4) contained in Filtrate 1 (E-15-1) andFiltrate 2 (G-15-1) were 0.4 g and 0 g, respectively.

In a similar manner to Example 1, Flat-plate molding (J-15-1) which wastransparent and pale yellow and from which no foreign substances wereobserved was obtained.

¹H-NMR measurement and analysis in a similar manner to Example 1revealed that the number of the rearrangement structures of the formula(9) per 100 main chain structures of the formula (10) was 0 in DriedProduct (F-15-1) and 0.003 in Film (I-15-1).

EXAMPLE 12

100 g of polyphenylene ether (A-1) and 2 g of modifier (B-5) werecharged in an autoclave, followed by nitrogen purging and hermeticalsealing in a similar manner to Example 1.

The amounts of (A-1) and (B-5) released out of the system upon pressurereduction and nitrogen purging were 0.6 g and 0.5 g, respectively.

The hermetically sealed autoclave was placed in an oil bath set at 130°C., followed by shaking for 5 minutes, whereby 100.0 g of Contents(C-16-1) were obtained in the powdery form.

From a 50 g portion of Contents (C-16-1), Wash 1 (D-16-1), Filtrate 1(E-16-1), 49.2 g of Dried substance 1 (F-16-1) and Filtrate 2 (G-16-1)were obtained in a similar manner to Example 1.

The amounts of modifier (B-5) contained in Filtrate 1 (E-16-1) andFiltrate 2 (G-16-1) were 0.5 g and 0 g, respectively.

In a similar manner to Example 1, Flat-plate molding (J-16-1) which wastransparent and pale yellow and from which no foreign substances wereobserved was obtained.

¹H-NMR measurement and analysis in a similar manner to Example 1revealed that the number of the rearrangement structures of theformula(9) per 100 main chain structures of the formula (10) was 0 inDried Product (F-16-1) and 0.004 in Film (I-16-1).

EXAMPLE 13

In a paddle drier (“NPD-16W Type”, trade name; product of Nara MachineryCo., Ltd.) equipped with a jacket for heating, 50 kg of polyphenyleneether (A-1) and 2 kg of modifier (B-1) were charged, followed bynitrogen charging inside of the paddle drier.

The jacket was heated to 200° C. over 1 hour by introducing thereintoheated steam.

After the temperature of the jacket reached 200° C., the jacket was keptat this temperature for 2 hours. Then, cool water was introduced intothe jacket for cooling.

From a 50 g portion of Contents (C-17-1), Wash 1 (D-17-1), Filtrate 1(E-17-1), 49.0 g of Dried substance 1 (F-17-1) and Filtrate 2 (G-17-1)were obtained in a similar manner to Example 1.

The amounts of modifier (B-1) contained in Filtrate 1 (E-17-1) andFiltrate 2 (G-17-1) were 0.3 g and 0 g, respectively.

In a similar manner to Example 1, Flat-plate molding (J-17-1) which wastransparent and pale yellow and from which no foreign substances wereobserved was obtained.

¹H-NMR measurement and analysis in a similar manner to Example 1revealed that the number of the rearrangement structures of the formula(9) per 100 main chain structures of the formula (10) was 0.001 in DriedProduct (F-17-1) and 0.0045 in Film (I-17-1).

EXAMPLE 14

In a Henschel mixer (“FM 500”, trade name; manufactured by Mitsui MiningCo. Ltd.) permitting jacket heating and cooling, 150 kg of polyphenyleneether (A-1) and 2 kg of modifier (B-1) were charged, followed by purgingwith nitrogen inside of the mixer.

A stirring blade was turned at a high speed and by shearing heat, thecontents were heated to 200° C. over 50 minutes.

After the internal temperature reached 200° C., high-speed rotation wascontinued for 5 minutes. Cool water was then introduced into the jacketfor cooling.

From a 50 g portion of Contents (C-18-1), Wash 1 (D-18-1), Filtrate 1(E-18-1), 49.3 g of Dried substance 1 (F-18-1) and Filtrate 2 (G-18-1)were obtained in a similar manner to Example 1.

The amounts of modifier (B-3) contained in Filtrate 1 (E-18-1) andFiltrate 2 (G-18-1) were 0.25 g and 0 g, respectively.

In a similar manner to Example 1, Flat-plate molding (J-18-1) which wastransparent and pale yellow and from which no foreign substances wereobserved was obtained.

¹H-NMR measurement and analysis in a similar manner to Example 1revealed that the number of the rearrangement structures of the formula(9) per 100 main chain structures of the formula (10) was 0.001 in DriedProduct (F-18-1) and 0.003 in Film (I-18-1).

EXAMPLE 15

In a Henschel mixer (“FM 500”, trade name; manufactured by Mitsui MiningCo., Ltd.) permitting jacket heating and cooling, 150 kg ofpolyphenylene ether (A-1) and 2 kg of modifier (B-1) were charged,followed by purging the inside with nitrogen.

A stirring blade was turned at a high speed and by shearing heat, thecontents were heated to 160° C. over 40 minutes.

After the internal temperature reached 160° C., the contents weretransferred to a 500-L hopper having an inside purged with nitrogen.After being allowed to stand for one day, they were taken out from thehopper.

From a 50 g portion of Contents (C-19-1), Wash 1 (D-19-1), Filtrate 1(E-19-1), 49 g of Dried substance 1 (F-19-1) and Filthrate 2 (G-19-1)were obtained in a similar manner to Example 1.

The amounts of modifier (B-1) contained in Filtrate 1 (E-19-1) andFiltrate 2 (G-19-1) were 0.15 g and 0 g, respectively.

In a similar manner to Example 1, Flat-plate molding (J-19-1) which wastransparent and pale yellow and from which no foreign substances wereobserved was obtained.

¹H-NMR measurement and analysis in a similar manner to Example 1revealed that the number of the rearrangement structures of the formula(9) per 100 main chain structures of the formula (10) was 0 in DriedProduct (F-19-1) and 0.002 in Film (I-19-1).

INDUSTRIAL APPLICABILITY

The modified polyphenylene ether resin of the invention has sufficientfunctionality and is well balanced between color tone/appearance andheat resistance/mechanical physical properties. The invention makes itpossible to provide the modified polyphenylene ether resin free ofproblems in equipment or energy upon preparation of it and can satisfythe demand of various industries.

1. A process for preparing a modified polyphenylene ether resin, whichcomprises: reacting a mixture of 100 parts by weight of (A) apolypheylene ether having a main chain structure of the followingformula (1)

wherein R₁ and R₄ each independently represents hydrogen, a primary orsecondary lower alkyl, a phenyl, an aminoalkyl or a hydrocarbonoxy, andR₂ and R₃ each independently represents hydrogen, a primary or secondarylower alkyl or phenyl, and 0.01 to 10 part by weight of (B) a modifierselected from the group consisting of conjugated non-aromatic dienecompounds, dienophilic compounds having one dienophile group andprecursors of the diene or dienophilic compounds at a temperature notlower than a room temperature and not higher than the melting point of(A) wherein the reaction to obtain the modified polyphenylene etherresin is carried out in a state where the polyphenylene ether is asolid.
 2. The process for preparing a modified polyphenylene ether resinaccording to claim 1, wherein the polyphenylene ether (A) is in the formof powder obtained by precipitation from a solution and has a meltingpoint of 240 to 260° C.
 3. The process for preparing a modifiedpolyphenylene ether resin according to claim 1, wherein the reactiontemperature is within a range of 100 to 230° C.
 4. The process forpreparing a modified polyphenylene ether resin according to claim 1,wherein the reaction temperature is within a range of 150 to 200° C. 5.The process for preparing a modified polyphenylene ether resin accordingto claim 1, wherein a paddle drier is employed upon preparation.
 6. Theprocess for preparing a modified polyphenylene ether resin according toclaim 1, wherein a Henschel mixer is employed upon preparation.
 7. Theprocess for preparing a modified polyphenylene ether resin according toclaim 1, wherein a hopper is employed upon preparation.
 8. The processfor preparing a modified polyphenylene ether resin according to claim 1,wherein the modified (B) is maleic anhydride, maleic acid, fumaric acid,phenyl maleimide, itaconic acid, malic acid, glycidyl acrylate orglycidyl methacrylate.
 9. The process for preparing a modifiedpolyphenylene ether resin to claim 1, wherein 0.2 to 3.0 parts by weightof the modifier (B) is reacted with 100 parts by weight of thepolyphenylene ether (A).